U.S. patent application number 14/727781 was filed with the patent office on 2016-12-01 for low fixing temperature sustainable toner.
This patent application is currently assigned to Xerox Corporation. The applicant listed for this patent is Xerox Corporation. Invention is credited to Guerino G Sacripante, Ke Zhou.
Application Number | 20160349642 14/727781 |
Document ID | / |
Family ID | 57282124 |
Filed Date | 2016-12-01 |
United States Patent
Application |
20160349642 |
Kind Code |
A1 |
Zhou; Ke ; et al. |
December 1, 2016 |
Low Fixing Temperature Sustainable Toner
Abstract
The disclosure relates to a resin made with no more than 6 mol %
of a rosin or a rosin derivative combined with a lower molecular
weight crystalline polyester resin in a toner with low fixing
temperature and higher blocking temperature.
Inventors: |
Zhou; Ke; (Oakville, CA)
; Sacripante; Guerino G; (Oakville, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Xerox Corporation |
Norwalk |
CT |
US |
|
|
Assignee: |
Xerox Corporation
|
Family ID: |
57282124 |
Appl. No.: |
14/727781 |
Filed: |
June 1, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G03G 9/08755
20130101 |
International
Class: |
G03G 9/087 20060101
G03G009/087 |
Claims
1. A toner comprising a bio-based polyester resin comprising no
more than 6 mole % of a mixture of a rosin-diol, a bis-rosin
alcohol and a rosin-carbonate; a crystalline polyester (CPE) resin,
wherein said CPE is comprised of an acid monomer and an alcohol
monomer, wherein said acid and alcohol monomers together comprise
16 or fewer methylene groups; an optional colorant; an optional
wax; and optionally, a resin monomer comprising bisphenol A (BPA),
wherein said toner comprises 0% BPA.
2. The toner of claim 1, wherein said mixture comprises some or all
rosin adducts I-V: ##STR00004## wherein R is a rosin moiety.
3. The toner of claim 1, wherein said CPE comprises a C10:C6
resin.
4. The toner of claim 1, wherein one ester unit obtained from an
alcohol monomer and an acid monomer of said CPE is represented by
the structure; ##STR00005##
5. The toner of claim 1, wherein said biobased resin comprises more
than 5 mol % of the mixture.
6. The toner of claim 1, wherein said CPE comprises dodecanedioic
acid.
7. The toner of claim 1, wherein said CPE comprises hexanediol.
8. The toner of claim 1, wherein said bio-based polyester resin
further comprises a polyacid, a polyol or both.
9. The toner of claim 1, wherein said bio-based polyester resin
further comprises fumaric acid, succinic acid, terephthalic acid or
isophthalic acid.
10. The toner of claim 1, wherein said bio-based polyester resin
comprises 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol,
1,4-butanediol or cyclohexanediol.
11. The toner of claim 1, comprising a fixing temperature of no
more than about 125.degree. C.
12. The toner of claim 1, comprising a blocking temperature of at
least about 53.degree. C.
13. The toner of claim 1, comprising a fixing latitude of at least
about 80.degree. C.
14. The toner of claim 1, wherein said resin comprises a
polydispersity of at least about 5.
15. The toner of claim 1, comprising a shell.
16. The toner of claim 1, further comprising an amorphous
resin.
17. The toner of claim 1, further comprising a colorant, a wax or
both.
18. A developer comprising the toner of claim 1.
19. The developer of claim 18, comprising a carrier.
20. The developer of claim 19, wherein said carrier comprises a
coating.
Description
FIELD
[0001] Sustainable resins comprising a rosin or a derivative
thereof and lower molecular weight crystalline polyester (CPE)
resins are combined and used in a toner to achieve resin
compatibility resulting in lower fixing temperature and higher
blocking temperature.
BACKGROUND
[0002] The vast majority of polymeric materials are based on
extracting and processing fossil fuels, a limited resource,
potentially resulting in accumulation of non-degradable materials
in the environment. Recently, the USDA proposed that all toner/ink
have a bio-derived (or sustainable) content of at least 20%.
Bio-derived resins are being developed but commercial integration
of such reagents into toner and ink remains to be resolved. (The
terms, "bio-derived resin," "bio-based resin," and, "sustainable
resin," are used interchangeably herein and are meant to indicate
that the resin or polyester resin is derived from or is obtained
from materials or reagents that are obtained from natural sources
and are biodegradable, in contrast to materials or monomers
obtained from petrochemicals or petroleum-based sources.)
[0003] Efforts to utilize crystalline resins with bio-based resins
result in blocking issues due to the higher plasticization rate of
CPE containing or made of monomers of a higher number of methylene
units, such as, using C10:C9 monomers with 10 and 9 methylene
units, respectively, in a CPE as compared to using a lower cost CPE
derived from C10:C6 monomers (with 10 and 6 methylene units,
respectively).
[0004] A bio-derived resin along with CPE comprising a lower number
of methylene units to produce toner exhibiting good blocking
characteristics without plasticization that addresses the problems
above is described.
SUMMARY
[0005] The instant disclosure describes a process for preparing a
sustainable resin using lower cost materials, such as, a
rosin-diol, and a CPE comprising smaller monomers with greater
resin compatibility resulting in toner with lower fix temperature
and higher blocking temperature.
[0006] In embodiments, a toner is disclosed including a resin
comprising no more than 6 mol % of a rosin or derivative thereof,
which resin is the product of reacting a rosin derivative, such as,
a rosin-diol and at least one alkylene glycol, and a crystalline
polyester (CPE) resin comprising lower molecular weight monomers
and optionally one or more components selected from a wax, a
colorant, an amorphous resin or combinations thereof, wherein the
CPE does not overly plasticize.
[0007] In embodiments, the amount of a rosin monomer in a bio-based
resin of interest is greater than 5 mol % and no more than 6 mole
%.
[0008] In embodiments, the resin monomer comprises a rosin-diol, a
bis-rosin alcohol, a rosin carbonate and isomers thereof.
[0009] A sustainable toner of lower fixing temperature and high
blocking temperature is comprised of a bioresin comprising no more
than 6 mol % of a rosin or derivative thereof and a CPE comprised
of lower molecular weight monomers. The resulting sustainable toner
comprises a mean fixing temperature of no more than 125.degree. C.
and a blocking temperature of at least about 53.degree. C.
[0010] In embodiments, the lower molecular weight CPE comprises
acid and alcohol monomers which together contain 16 or fewer
methylene groups.
DETAILED DESCRIPTION
[0011] Glycerine carbonate (C.sub.4H.sub.6O.sub.4) can be reacted
with an organic acid, such as, a rosin acid, to make alcohols, such
as, rosin-diols (denoted in the figure below as I and II), as well
as bis-rosin alcohols (identified as III and IV below) and a
rosin-carbonate (identified as V below), as depicted in the
following scheme.
##STR00001##
[0012] The resulting mixture of rosin adducts I through V can vary
in relative amounts depending on, for example, reaction conditions,
stoichiometry of the starting rosin acid, glycerine carbonate
amount and catalyst. In an embodiment, of from about 1.0 to about
1.2 mole equivalents of rosin acid are reacted with from about 1.2
to about 3 mole equivalents of glycerine carbonate and a catalyst,
such as, tetralkyl ammonium halide, at a temperature of from about
140.degree. to about 170.degree. C. The excess glycerine carbonate
can be distilled from the reaction mixture, if desired.
[0013] The relative ratio of rosin-diol (I and II) amount to
bis-rosin alcohol (III and IV) amount can vary of from about 3:1 to
about 20:1 when excess glycerine carbonate is utilized as more
rosin diol is produced.
[0014] Rosin adducts I through V then can be reacted with known
polyester-forming monomers, for example, terephthalic acid or
succinic acid, and other polyols, such as, butanediol or
1,2-propylene glycol, in a polycondensation reaction to form a
resin. Rosin-diols I and II, as well as rosin-carbonate V
polymerize with polyacids to form the backbone of a polyester
resin, and bis-rosin alcohols III and IV can form terminal groups
(moieties) of a polyester resin, as depicted, for example, in the
following structure
##STR00002##
wherein R is a rosin moiety, R.sub.1 is an alkyl or aryl moiety,
segments I to IV represent the rosin adduct moieties, and n and m
represent the number of individual, single acid/alcohol ester units
and each of n and m is from about 10 to about 10,000.
[0015] The ratio of rosin-diols to bis-rosin alcohols influences
polydispersity of a resin. If the ratio of rosin-diols to bis-rosin
alcohols is high, such as, from about 10:1, from about 15:1, from
about 20:1 or more, polydispersity of the polymer, as measured as
the ratio of weight average (M.sub.w) to number average (M.sub.n)
molecular weight, is relatively low, such as, from about 2 to 4.
However, if the ratio of rosin-diols to bis-rosin alcohols is
lower, such as, from about 6:1, from about 5:1, from about 4:1 or
lower, polydispersity of the polymer is relatively high, such as,
from 5 to about 40.
[0016] To obtain a toner resin with optimal fusing performance,
including broad fusing latitude, a toner comprises relative high
polydispersity, such as, at least about 5, at least about 7.5, at
least about 10, up to about 15, up to about 17.5, up to about 20 or
more, which can be obtained with rosin adduct mixtures comprising
lower amounts of rosin diols, which can be obtained using lower
amounts of, for example, glycerol carbonate when reacted with a
rosin acid to form said adducts.
[0017] Processes to obtain a lower cost sustainable resin, where
rosin adducts for producing resin reagents are made from glycerine
carbonate and rosin acid are disclosed. In embodiments, to optimize
compatibility of a rosin-based resin with a lower cost crystalline
resin comprising smaller acid/ester and alcohol monomers, such as,
for example, poly(1,6-hexylene-dodecanoate), CPE 10:6, the amount
of rosin-derived monomer in the bioresin is no more than 6 mol % of
the bioresin such that compatibility (as revealed, for example, by
degree of plasticization) is not too high or too low. To obtain
polyester toners with low fixing temperatures and good blocking
(cohesion) performance, a mixture of amorphous polyester resins and
crystalline polyester resin is at least partially compatible as
revealed, for example, by desired toner properties, such as, MFT
and blocking performance. If the resulting toner is comprised of an
amorphous, biobased polyester resin and a crystalline resin that
are too compatible, low fixing temperature is obtained, but that
high resin compatibility results in too much plasticization
resulting in poor blocking performance. Conversely, if a toner is
comprised of an amorphous, biobased polyester resin and a
crystalline resin that are not too compatible or incompatible, good
blocking performance will be obtained but fixing temperature will
be higher. Therefore, to obtain both good blocking and low fixing
temperature, an optimal compatibility between the amorphous and
crystalline resins is desired.
[0018] By good blocking performance, as determined practicing known
methods, see, for example, U.S. Pat. No. 7,910,275, herein
incorporated by reference in entirety, is a toner with a blocking
temperature of at least about 50.degree. C., at least about
53.degree. C., at least about 54.degree. C., at least about
55.degree. C., at least about 56.degree. C. or higher.
[0019] By good minimum fixing temperature (MFT), as determined
practicing known methods, see, for example, U.S. Pat. No.
7,291,437, herein incorporated by reference in entirety, is a toner
with a fixing temperature of no more than about 125.degree. C., no
more than about 124.degree. C., no more than about 123.degree. C.,
no more than about 122.degree. C. or lower.
[0020] Fusing (or fixing) latitude is the value obtained when
minimum fixing temperature is subtracted from the hot offset
temperature, as determined practicing known methods, see, for
example, U.S. Pat. No. 7,291,437, herein incorporated by reference
in entirety. In a toner of interest, good latitude is at least
about 80.degree. C., at least about 82.5.degree. C., at least about
85.degree. C. or higher.
[0021] Unless otherwise indicated, all numbers expressing
quantities and conditions, and so forth used in the specification
and claims are to be understood as being modified in all instances
by the term. "about." "About," is meant to indicate a variation of
no more than 10% from the stated value. Also used herein is the
term, "equivalent," "similar," "essentially," "substantially,"
"approximating" and "matching," or grammatical variations thereof,
have generally acceptable definitions or at the least, are
understood to have the same meaning as, "about."
[0022] As used herein, a polymer is defined by the monomer(s) from
which a polymer is made. Thus, for example, while in a polymer made
using terephthalic acid as a monomer reagent, a terephthalic acid
moiety per se no longer exists because of the ester condensation
reaction, as used herein, that polymer is said to comprise a
terephthalic acid. Thus, a biopolymer made by a one-pot process
disclosed herein can comprise terephthalate/terephthalic acid;
succinic acid; neopentyl glycol and dehydroabietic acid. That
biopolymer also can be said to comprise neopentyl glycol as that
diol is used with the terephthalate/terephthalic acid and succinic
acid; can be said to comprise terephthalic acid as that monomer was
used to make the biopolymer; can be said to be composed of or as
comprising succinic acid as succinic acid is a monomer reagent of
that polymer and so on. Hence, a polymer is defined herein based on
one or more of the component monomer reagents, which provides a
means to name a polymer of interest and to define and to identify a
polymer of interest.
[0023] As used herein, "biobased," or use of the prefix, "bio,"
refers to a reagent or to a product that is composed, in whole or
in part, of a biological product, including plant, animal and
marine materials, or derivatives thereof. Generally, a biobased or
biomaterial is, "biodegradable," that is, substantially or
completely biodegradable, by substantially is meant greater than
50%, greater than 60%, greater than 70% or more of the material is
degraded from the original molecule to another form by a biological
or environmental mechanism, such as, action thereon by bacteria,
animals, plants, light, temperature, oxygen and so on in a matter
of days, matter of weeks, a year or more, but generally no longer
than two years. A, "bioresin," is a resin, such as, a polyester,
which contains or is composed of a biobased material in whole or in
part, such as, a polyglycol, such as, polyethylene glycol and a
dicarboxylic acid. Hence, the reagents can be a biopolyacid and a
biopolyol. Such a reagent or resin can be described as,
"sustainable," a synonym of bio-based.
[0024] In embodiments, a sustainable toner of interest is one which
replaces one or more limited, hazardous or petroleum-based reagents
with one that is not, one that is sustainable or bio-based. One
such less than desired reagent or compound found in commercial
toner is bisphenol A (BPA). BPA is considered a possible
carcinogen, a compound that could precipitate a number of health
issues and one believed to have estrogen activity. Hence, a
suitable sustainable toner of interest would be one which replaces
some or all BPA-containing reagents with a bio-based reagent, with
minimal or no loss of toner performance. Hence, when BPA amount is
reduced or removed altogether and replaced with one or more
bioreagents, such a sustainable toner is one which is BPA-free,
contains no or 0% BPA and other functionally equivalent phrases and
terms.
[0025] As used herein, "plasticize," including grammatical
variations thereof, refers to a change in the thermal and
mechanical properties of a given polymer which involves: (a)
lowering of rigidity at room temperature (RT); (b) lowering of
temperature at which substantial deformations can occur with not
too large forces; (c) increase of the elongation to break at RT;
and/or (d) increase of toughness (impact strength) down to the
lowest temperature of serviceability. For example, a plasticizer
lowers T.sub.g of a polymer or negatively impacts blocking
(cohesion) of a toner in which a plasticizer is present.
[0026] As used herein, a, "rosin," or, "rosin adduct," or grammatic
forms thereof is intended to encompass a rosin, a rosin acid, a
rosin ester, a rosin-diol, a rosin carbonate, a bis-rosin alcohol
and so on, as well as a rosin derivative which is a rosin treated,
for example, to comprise plural alcohol groups that can be used
directly or indirectly as a monomer in a polyester polymer. Hence,
a rosin derivative is a compound that is an acid, ester or alcohol
that can be used to form a polyester polymer. As known in the art,
rosin is a blend of at least eight monocarboxylic acids. Abietic
acid can be a primary species and the other seven acids are isomers
thereof. Because of the composition of a rosin, often the synonym,
"rosin acid," is used to describe various rosin-derived products.
As known, rosin is not a polymer but essentially a varying blend of
the eight species of carboxylic acids. A rosin product includes, as
known in the art, chemically modified rosin, such as, partially or
fully hydrogenated rosin acids, partially or fully dimerized rosin
acids, esterified rosin acids, functionalized rosin acids or
combinations thereof. Rosin is available commercially in a number
of forms, for example, as a rosin acid, as a rosin ester and so on.
For example, rosin acids, rosin ester and dimerized rosin are
available from Eastman Chemicals under the product lines,
POLY-PALE.TM., DYMEREX.TM., STAYBELITE-E.TM., FORAL.TM. Ax-E,
LEWISOL.TM. and PENTALYN.TM.; Arizona Chemicals under the product
lines, SYLVALITE.TM. and SYLVATAC.TM.; and Arakawa-USA under the
product lines, Pensel and Hypal. In embodiments, rosin adducts are
compounds I-V depicted hereinabove.
[0027] The designation, "CX:CY," "CX:Y," "X:Y," and forms thereof
as used herein describe crystalline resins, wherein C is carbon, X
is a positive, non-zero integer identifying the number of methylene
groups of the acid/ester monomer used to produce the CPE and Y is a
positive, non-zero integer identifying the number of methylene
groups of the alcohol monomer used to produce the CPE. Thus, for
example, C10 can represent, for example, a dodecanedioic acid and
C6 can represent, for example, a hexanediol. X and Y each is 10 or
lower. In embodiments, the sum of X and Y is 16 or lower.
[0028] For example, a rosin acid or polyacidic forms thereof can be
reacted with a polyol in a condensation reaction where the hydroxyl
group of the alcohol combines at a carboxylic acid group of a rosin
acid in a condensation reaction to form a joined molecule, a rosin
ester, which is a, "single ester unit," composed of one alcohol
monomer joined to one acid/ester monomer, which dimer can be viewed
as a "monomer" or subunit when plural copies of that dimer are
joined to form a polymer. Additional acid, ester alcohol and/or
acid/alcohol monomers are added to the single ester unit to form a
polyester polymer. Such a reaction is compatible with one-pot
reaction conditions disclosed herein for producing a bioresin.
[0029] In embodiments, the reactions as disclosed herein result in,
in part, abieticdiol, abietic monoglycerate, palustricdiol,
palustric monoglycerate, dehydroabieticdiol, dehydroabietic
monoglycerate, neoabieticdiol, neoabietic monoglycerate,
levopimaricdiol, levopimaric monoglycerate, pimaricdiol, pimaric
monoglycerate, sandaracopimaricdiol, sandaracopimaric
monoglycerate, isopimaricdiol, isopimaric monoglycerate,
hydrogenated abieticdiol, hydrogenated palustricdiol, hydrogenated
dehydroabieticdiol, hydrogenated neoabieticdiol, hydrogenated
levopimaricdiol, hydrogenated pimaricdiol, hydrogenated
sandaracopimaricdiol, hydrogenated isopimaricdiol and so on.
[0030] A catalyst can be included in the reaction mixture to form
an ester unit or a polyester polymer. Suitable catalysts include
organoamines, such as, ethylamine, butylamine and propylamine,
arylamines, such as, imidazole, 2-methyl imidazole, pyridine and
dimethylamino pyridine, organoammonium halides, such as,
trimethylammonium chloride, triethylammonium chloride,
tributylammonium chloride, trimethylammonium bromide,
triethylammonium bromide, tributylammonium bromide,
trimethylammonium iodide, triethylammonium iodide, tributylammonium
iodide, tetraethylammonium chloride, tetraethylammonium bromide and
tetraethylammonium iodide, organophosphines, such as,
triphenylphosphine, organophosphonium halides, such as,
tetraethylphosphonium chloride, tetraethylphosphonium bromide,
tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide,
tetrabutyl phosphonium iodide and so on.
[0031] The reaction can be conducted at an elevated temperature,
such as, from about 130.degree. C. to about 200.degree. C., from
about 145.degree. C. to about 175.degree. C., from about
150.degree. C. to about 170.degree. C. and so on, although
temperatures outside of those ranges can be used as a design
choice.
[0032] In embodiments, a bio-based resin of interest comprises
rosin or a derivative thereof, for example, one or more of rosin
adducts I through V as depicted above, in an amount no more than 6
mol %. In an aspect, 8 mol % or greater of a rosin reagent in a
resin results in excessive plasticization (compatibility) of the
bio-based resin with a lower molecular weight CPE, resulting, for
example, with poor blocking performance. Conversely, 5 mole % or
less of rosin reagent results in insufficient plasticization
(compatibility) of the rosin-containing bio-based resin when
combined with a lower molecular weight CPE, such as, C10:C6. In
embodiments, such rosin adducts or derivatives are present in a
bioresin in an amount greater than 5 mol % but no more than 6 mol
%.
[0033] Toner Particles
[0034] A toner composition can comprise more than one form or sort
of polymer, such as, two or more different polymers, such as, two
or more different polyester polymers composed of different
monomers, where at least one of the polymers is a rosin-containing
biopolymer or bioresin of interest. The polymer can be an
alternating copolymer, a block copolymer, a graft copolymer, a
branched copolymer, a crosslinked copolymer and so on.
[0035] The toner particle can include other optional reagents, such
as, a surfactant, a wax, a colorant, a shell and so on. The toner
composition optionally can comprise inert particles, which can
serve as toner particle carriers, which can comprise a
rosin-containing resin taught herein. The inert particles can be
modified, for example, the surface thereof can be derivatized or
the particles can be manufactured for a desired purpose, for
example, to carry a charge or to possess a magnetic field.
[0036] A. Components
[0037] 1. Resin
[0038] The biopolyester of interest is used alone with a CPE of
interest or in combination with one or more other known resins used
in toner with a CPE of interest.
[0039] One, two or more polymers in addition to a biopolymer and
CPE of interest may be used in forming a toner or toner particle.
When additional polymers are used, the polymers may be in any
suitable ratio (e.g., weight ratio) such as, for instance, with two
different polymers, from about 1% (biopolymer)/99% (second polymer)
to about 99% (biopolymer)/1% (second polymer), or outside of those
ranges as a design choice. For example, a toner can comprise two
forms of amorphous polyester resins, one of which is a biopolymer
of interest, and a crystalline resin as taught herein, in relative
amounts as a design choice.
[0040] a. Polyester Resins
[0041] The ratio of crystalline polyester resin to amorphous
polyester resins, including a rosin-containing polyester resin of
interest, can be in the range from about 1:99 to about 30:70; from
about 5:95 to about 25:75; from about 5:95 to about 15:85.
[0042] A polyester resin may be obtained synthetically, for
example, in an esterification reaction involving a reagent
comprising plural acid or ester groups and another reagent
comprising alcohol with plural hydroxyl groups, in embodiments, an
acid/ester monomer and an alcohol monomer.
[0043] In embodiments, the alcohol reagent comprises one or two or
more hydroxyl groups, three or more hydroxyl groups. In
embodiments, the acid/ester monomer comprises two or more acid or
ester groups, three or more acid or ester groups. Reagents
comprising three or more functional groups enable, promote or
enable and promote polymer branching and crosslinking. Reagents
that contain one hydroxyl group can contain a reactive ester group
or can promote resin end capping.
[0044] Examples of polyacids or polyesters, which may be a bioacid
or a bioester, that can be used for preparing an amorphous
polyester resin include terephthalic acid, phthalic acid,
isophthalic acid, fumaric acid, trimellitic acid, diethyl fumarate,
dimethyl itaconate, cis-1,4-diacetoxy-2-butene, dimethyl fumarate,
diethyl maleate, maleic acid, succinic acid, itaconic acid,
succinic acid, cyclohexanoic acid, succinic anhydride,
dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid,
glutaric anhydride, adipic acid, pimelic acid, suberic acid,
azelaic acid, dodecanedioic acid, dimethyl
naphthalenedicarboxylate, dimethyl terephthalate, diethyl
terephthalate, dimethylisophthalate, diethylisophthalate,
dimethylphthalate, phthalic anhydride, diethylphthalate,
dimethylsuccinate, naphthalene dicarboxylic acid, dimer diacid,
dimethylfumarate, dimethylmaleate, dimethylglutarate,
dimethyladipate, dimethyl dodecylsuccinate, and combinations
thereof. The polyacid or polyester reagent may be present, for
example, in an amount from about 40 to about 60 mol % of the resin,
irrespective of the number of species of acid or ester monomers
used.
[0045] Examples of polyols which may be used in generating an
amorphous polyester resin include rosin-diols, bis-rosin alcohols,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol
1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol,
2,2,3-trimethylhexanediol, dodecanediol, 1,4-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, heptanediol, xylenedimethanol,
cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide,
dipropylene glycol, dibutylene glycol and combinations thereof. The
amount of polyol can vary, and may be present, for example, in an
amount from about 40 to about 60 mol % of the resin.
[0046] For forming a crystalline polyester resin, suitable polyols
include aliphatic polyols with from about 2 to about 12 carbon
atoms, with no more than 10 methylene groups, such as,
1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,
2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol
and the like. The polyol may be, for example, selected in an amount
from about 40 to about 60 mol %.
[0047] Examples of polyacid or polyester reagents for preparing a
crystalline resin include reagents of from about 2 to about 12
carbon atoms, with no more than 10 methylene groups, such as,
oxalic acid, succinic acid, glutaric acid, adipic acid, suberic
acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate,
dimethyl itaconate, cis-1,4-diacetoxy-2-butene, diethyl fumarate,
diethyl maleate, phthalic acid, isophthalic acid, 1,10 decanedioic
acid, 1,11-undecanedioic acid, 1,9-nonanedioic acid,
1,12-dodecanedioic acid, terephthalic acid,
naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic
acid, cyclohexane dicarboxylic acid (sometimes referred to herein,
in embodiments, as cyclohexanedioic acid), malonic acid and
mesaconic acid, a polyester or anhydride thereof. The polyacid may
be selected in an amount of, for example, in embodiments, from
about 40 to about 60 mol %.
[0048] Specific crystalline resins that can be used include
poly(ethylene-adipate), poly(propylene-adipate),
poly(butylene-adipate), poly(pentylene-adipate),
poly(hexylene-adipate), poly(octylene-adipate),
poly(ethylene-succinate), poly(propylene-succinate),
poly(butylene-succinate), poly(pentylene-succinate),
poly(hexylene-succinate), poly(octylene-succinate),
poly(ethylene-sebacate), poly(propylene-sebacate),
poly(butylene-sebacate), poly(pentylene-sebacate),
poly(hexylene-sebacate), poly(octylene-sebacate),
poly(decylene-sebacate), poly(decylene-decanoate),
poly(ethylene-decanoate), poly(ethylene dodecanoate),
poly(1,6-hexylene-decanoate), poly(1,6-hexylene dodecanoate),
poly(nonylene-sebacate), poly(nonylene-decanoate),
copoly(ethylene-fumarate)-copoly(ethylene-sebacate),
copoly(ethylene-fumarate)-copoly(ethylene-decanoate),
copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate) and
copoly(2,2-dimethylpropane-1,3-diol-decanoate)-copoly(ethylene-adipate).
[0049] A suitable CPE resin may include a resin of
1,12-dodecanedioic acid and 1,6-hexanediol monomers, where such CPE
resin is denoted a C10:6, where the integers represent the number
of methylene units (e.g., C10, ten methylene units and C6, six
methylene units) in the reagents, single ester unit and polyester
polymer.
[0050] A suitable CPE is one which has as a basic ester unit,
composed of an alcohol monomer and an acid/ester monomer joined by
an ester condensation reaction to form a dimer, where said dimer is
repeated in a polyester polymer, where the dimer can be viewed as a
monomer of the polymer, the unit having the following
structure:
##STR00003##
[0051] The crystalline resin may be present, for example, in an
amount from about 1 to about 25% by weight of the toner components,
from about 2 to about 20% by weight of the toner components, from
about 3 to about 15% by weight of the toner components. The
crystalline resin can possess various melting points of, for
example, from about 30.degree. C. to about 120.degree. C., from
about 50.degree. C. to about 90.degree. C., from about 60.degree.
C. to about 80.degree. C. The crystalline resin may have a number
average molecular weight (M.sub.n), as measured by gel permeation
chromatography (GPC) of, for example, from about 1,000 to about
50,000, from about 2,000 to about 25,000, and a weight average
molecular weight (M.sub.w) of, for example, from about 2,000 to
about 100,000, from about 3,000 to about 80,000, as determined by
GPC. The molecular weight distribution (M.sub.w/M.sub.n or
polydispersity) of the crystalline resin may be, for example, from
5 to about 40, from about 6 to about 35, or outside of those ranges
and at least greater than 5.
[0052] b. Esterification Catalyst
[0053] Condensation catalysts may be used in a polyester reaction
and include those disclosed hereinabove, and tetraalkyl titanates;
dialkyltin oxides, such as, dibutyltin oxide; tetraalkyltins, such
as, dibutyltin dilaurate; dibutyltin diacetate; dibutyltin oxide;
dialkyltin oxide hydroxides, such as, butyltin oxide hydroxide;
aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous
oxide, stannous chloride, butylstannoic acid or combinations
thereof.
[0054] Such catalysts may be used in amounts of, for example, from
about 0.01 mole % to about 5 mole % based on the amount of starting
polyacid, polyol or polyester reagent in the reaction mixture.
[0055] c. Branching/Crosslinking
[0056] Branching agents can be used and include, for example, a
multivalent polyacid, such as, 1,2,4-benzene-tricarboxylic acid,
1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic
acid, 1,2,4-naphthalenetricarboxylic acid,
1,2,5-hexanetricarboxylic acid,
1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane,
tetra(methylene-carboxyl)methane, 1,2,7,8-octanetetracarboxylic
acid, acid anhydrides thereof, lower alkyl esters thereof and
multivalent polyols, such as, glycerine, pentaerythritol, glycerine
carbonate, trimethylopropane and so on. A branching agent can be
used in an amount from about 0.01 to about 10 mole % of the resin,
although amounts outside of that range can be used.
[0057] d. Process
[0058] Hence, suitable polyacids/polyesters and polyols, which may
be biodegradable, are combined under suitable conditions, as known
in the art, such as, mixed at RT, generally, from about 20.degree.
C. to about 25.degree. C., and then heated to an elevated
temperature, under atmospheric or inert gas conditions, under
reduced or elevated pressure as known in the art and so on, as a
design choice. The esterification reaction generally produces water
or an alcohol byproduct, which can be removed practicing known
materials and methods, such as, distillation.
[0059] For example, as known in the art, the polyacid/polyester and
polyol reagents, including dipropylene glycol, are mixed together,
optionally with a catalyst, and incubated at an elevated
temperature, such as, from about 200.degree. C. or more, from about
210.degree. C. or more, from about 220.degree. C. or more, and so
on, but sometimes not more than about 230.degree. C., not more than
about 235.degree. C. or more, although temperatures outside of
those ranges can be used to enable esterification to proceed to
equilibrium, which generally yields water or an alcohol as a
byproduct, such as, methanol, arising from forming the ester bonds
in esterification reactions. Temperatures above 230.degree. C. may
result in volatilization of some reagents, for example, dipropylene
glycol, and removal of that reagent can moderate a condensation
reaction, and hence, the acid value (AV) of the developing polymer.
The reaction can be conducted under vacuum to promote
polymerization and to facilitate removal of any volatilized
reagents. The reaction can be conducted under an inert atmosphere,
such as, nitrogen gas, again, which can facilitate removal of any
volatilized reagents.
[0060] To provide latitude in manipulating reaction conditions to
obtain resins with the desired softening temperature (T.sub.g) and
AV, a stoichiometric imbalance of polyacid to polyol can be
utilized, and generally, the polyacid is in excess unless the
polyol is volatile and distills from the mixture. An excess of a
reagent can be determined in terms of stoichiometric excess of
alcohol to acid in the reaction mixture. That can be assessed in
terms of molar equivalents such that the molar ratio of
alcohol:acid is greater than 0.5:0.5, for example, from about 0.505
to about 0.495, from about 0.51 to about 0.49, from about 0.515 to
about 0.485, from about 0.52 to about 0.48 or greater amounts of
alcohol relative to acid. When another alcohol is included in the
reaction, the molar equivalents of the alcohols are summed for the
above calculation.
[0061] Accordingly, disclosed herein is one-pot reaction for
producing a biopolyester resin suitable for use in an imaging
toner. A biopolyester resin is produced and processed to form a
polymer reagent, which can be dried and formed into flowable
particles, such as, a pellet, a powder and the like. The polymer
reagent then can be incorporated with, for example, other reagents
suitable for making a toner particle, such as, a colorant and/or a
wax, and processed in a known manner to produce toner
particles.
[0062] Polyester resins suitable for use in an imaging device can
carry one or more properties, such as, a glass transition
temperature (T.sub.g)(onset) of at least about 50.degree. C., at
least about 53.degree. C., at least about 55.degree. C.; a T.sub.g
of at least about 110.degree. C., at least about 120.degree. C., at
least about 125.degree. C.; an AV of at least about 8, at least
about 12 mg of KOH/g, at least about 15 mg of KOH/g, or an AV from
about 8 to about 18 mg of KOH/g, from about from about 11 to about
17 mg of KOH/g, from about 10 to about 16 mg of KOH/g; an M.sub.W
of at least about 10,000 g/mol, at least about 25,000 g/mol, at
least about 60,000 g/mol; and an Mn of at least about 50,000 g/mol,
at least about 10,000 g/mol, at least about 15,000 g/mol.
[0063] 2. Colorants
[0064] Suitable colorants include a carbon black, such as, REGAL
330.RTM. and Nipex 35; magnetites, such as, Mobay magnetites,
MO8029.TM. and MO8060.TM.; Columbian magnetites, MAPICO.RTM. BLACK;
surface-treated magnetites; Pfizer magnetites, CB4799.TM.,
CB5300.TM., CB5600.TM. and MCX6369.TM.; Bayer magnetites, BAYFERROX
8600.TM. and 8610.TM.; Northern Pigments magnetites, NP-604.TM. and
NP-608.TM.; Magnox magnetites, TMB-100.TM. or TMB-104.TM.; and the
like.
[0065] Colorants, such as, cyan, magenta, yellow, red, orange,
green, brown, blue or mixtures thereof can be used. Colorants can
be used as water-based pigments.
[0066] Examples of other colorants include SUNSPERSE 6000,
FLEXIVERSE and AQUATONE, water-based pigment dispersions from SUN
Chemicals; HELIOGEN BLUE L6900.TM., D6840.TM., D7080.TM.,
D7020.TM., PYLAM OIL BLUE.TM., PYLAM OIL YELLOW.TM. and PIGMENT
BLUE 1.TM. available from Paul Uhlich & Company, Inc.; PIGMENT
VIOLET I.TM., PIGMENT RED 48.TM., LEMON CHROME YELLOW DCC IO26.TM.,
TOLUIDINE RED.TM. and BON RED C.TM. available from Dominion Color
Corporation, Ltd., Toronto, Ontario; NOVAPERM YELLOW FGL.TM. from
Hoechst; CINQUASIA MAGENTA.TM. available from E.I. DuPont de
Nemours & Co., and the like.
[0067] Examples of magenta colorants include
2,9-dimethyl-substituted quinacridone, an anthraquinone dye
identified in the Color Index as CI 60710, CI Dispersed Red 15, a
diazo dye identified in the Color Index as CI 26050, CI Solvent Red
19 and the like.
[0068] Illustrative examples of cyan colorants include copper
tetra(octadecylsulfonamido) phthalocyanine, a copper phthalocyanine
pigment listed in the Color Index as CI 74160, CI Pigment Blue,
Pigment Blue 15:3, Pigment Blue 15:4, an Anthrazine Blue identified
in the Color Index as CI 69810, Special Blue X-2137 and the
like.
[0069] Illustrative examples of yellow colorants are diarylide
yellow 3,3-dichlorobenzidene acetoacetanilide, a monoazo pigment
identified in the Color Index as CI 12700, CI Solvent Yellow 16, a
nitrophenyl amine sulfonamide identified in the Color Index as
Foron Yellow SE/GLN, CI Disperse Yellow 3 and
2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxy
acetoacetanilide.
[0070] Other known colorants can be used, such as, Levanyl Black
A-SF (Miles, Bayer) and Sunsperse Carbon Black LHD 9303 (Sun
Chemicals), and colored dyes, such as, Neopen Blue (BASF), Sudan
Blue OS (BASF). PV Fast Blue B2G 01 (American Hoechst), Sunsperse
Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA (CibaGeigy),
Paliogen Blue 6470 (BASF), Sudan III (Matheson, Coleman, Bell),
Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman,
Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF). Paliogen
Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen
Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol
Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1
(Hoechst), Permanent Yellow YE 0305 (Paul Uhlich), Lumogen Yellow
D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), Suco-Gelb
L1250 (BASF), SUCD-Yellow D01355 (BASF), Hostaperm Pink E (American
Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (DuPont),
Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for
Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Toluidine
Red (Aldrich), Lithol Rubine Toner (Paul Uhlich), Lithol Scarlet
4440 (BASF), Bon Red C (Dominion Color Company), Royal Brilliant
Red RD-8192 (Paul Uhlich), Oracet Pink RF (Ciba-Geigy), Paliogen
Red 3871K (BASF), Paliogen Red 3340 (BASF), Lithol Fast Scarlet
L4300 (BASF), combinations of the foregoing and the like. Other
colorants that can be used, and which are commercially available
include various colorants in the color classes, Pigment Yellow 74,
Pigment Yellow 14, Pigment Yellow 83, Pigment Orange 34, Pigment
Red 238, Pigment Red 122, Pigment Red 48:1, Pigment Red 269,
Pigment Red 53:1, Pigment Red 57:1, Pigment Red 83:1, Pigment
Violet 23, Pigment Green 7 and so on, and combinations thereof.
[0071] In general, colorant may be employed in an amount ranging
from 0% (colorless or clear) to about 35% by weight of the toner
particles on a solids basis.
[0072] 3. Optional Components
[0073] a. Surfactants
[0074] Toner compositions or reagents therefor may be in
dispersions or emulsions including a surfactant. Emulsion
aggregation (EA) methods where the polymer and other components of
the toner are in combination or are in an aqueous or organic medium
can employ one or more surfactants to form an emulsion.
[0075] One, two or more surfactants may be used. The surfactants
may be selected from ionic surfactants and nonionic surfactants, or
combinations thereof. Anionic surfactants and cationic surfactants
are encompassed by the term, "ionic surfactants."
[0076] In embodiments, the surfactant or the total amount of
surfactants may be used in an amount of from about 0.01% to about
5% by weight of the reagents in a composition.
[0077] Examples of nonionic surfactants include, for example,
polyoxyethylene cetyl ether, polyoxyethylene lauryl ether,
polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether,
polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate,
polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether
and dialkylphenoxy poly(ethyleneoxy) ethanol, for example,
available from Rhone-Poulenc as IGEPAL CA-210.TM., IGEPAL
CA-520.TM., IGEPAL CA-720.TM., IGEPAL CO-290.TM., IGEPAL
CA-210.TM., ANTAROX 890.TM. and ANTAROX 897.TM.. Other examples of
suitable nonionic surfactants include a block copolymer of
polyethylene oxide and polypropylene oxide, including those
commercially available as SYNPERONIC.RTM. PR/F, in embodiments,
SYNPERONIC.RTM. PR/F 108; and a DOWFAX, available from The Dow
Chemical Corp.
[0078] Anionic surfactants include sulfates and sulfonates, such
as, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate,
sodium dodecylnaphthalene sulfate and so on; dialkyl benzenealkyl
sulfates; acids, such as, palmitic acid, and NEOGEN or NEOGEN SC
obtained from Daiichi Kogyo Seiyaku, and so on, combinations
thereof and the like. Other suitable anionic surfactants include,
in embodiments, alkyldiphenyloxide disulfonates or TAYCA POWER
BN2060 from Tayca Corporation (Japan), which is a branched sodium
dodecyl benzene sulfonate. Combinations of those surfactants and
any of the foregoing nonionic surfactants may be used in
embodiments.
[0079] Examples of cationic surfactants include, for example,
alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl
ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl
methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide,
benzalkonium chloride, cetyl pyridinium bromide, trimethyl ammonium
bromides, halide salts of quarternized polyoxyethylalkylamines,
dodecylbenzyl triethyl ammonium chlorides, MIRAPOL.RTM. and
ALKAQUAT.RTM. available from Alkaril Chemical Company, SANISOL.RTM.
(benzalkonium chloride) available from Kao Chemicals and the like,
and mixtures thereof, including, for example, a nonionic surfactant
as known in the art or provided hereinabove.
[0080] b. Waxes
[0081] The toners of the instant disclosure, optionally, may
contain a wax, which can be either a single type of wax or a
mixture of two or more different types of waxes (hereinafter
identified as, "a wax"). When included, the wax may be present in
an amount of, for example, from about 1 wt % to about 25 wt % of
the toner particles. Waxes that may be selected include waxes
having, for example, an M.sub.w of from about 500 to about
20,000.
[0082] Waxes that may be used include, for example, polyolefins,
such as, polyethylene, polypropylene and polybutene waxes, such as,
those that are commercially available, for example, POLYWAX.TM.
polyethylene waxes from Baker Petrolite, wax emulsions available
from Michaelman, Inc. or Daniels Products Co., EPOLENE N15.TM.
which is commercially available from Eastman Chemical Products,
Inc., VISCOL 550-P.TM., a low weight average molecular weight
polypropylene available from Sanyo Kasei K. K.; plant-based waxes,
such as carnauba wax, rice wax, candelilla wax, sumac wax and
jojoba oil; animal-based waxes, such as beeswax; mineral-based
waxes and petroleum-based waxes, such as montan wax, ozokerite,
ceresin wax, paraffin wax, microcrystalline wax and Fischer-Tropsch
waxes; ester waxes obtained from higher fatty acids and higher
alcohols, such as stearyl stearate and behenyl behenate; ester
waxes obtained from higher fatty acids and monovalent or
multivalent lower alcohols, such as butyl stearate, propyl oleate,
glyceride monostearate, glyceride distearate and pentaerythritol
tetrabehenate; ester waxes obtained from higher fatty acids and
multivalent alcohol multimers, such as diethyleneglycol
monostearate, dipropyleneglycol distearate, diglyceryl distearate
and triglyceryl tetrastearate; sorbitan higher fatty acid ester
waxes, such as sorbitan monostearate; cholesterol higher fatty acid
ester waxes, such as, cholesteryl stearate, and so on.
[0083] Examples of functionalized waxes that may be used include,
for example, amines and amides, for example, AQUA SUPERSLIP
6550.TM. and SUPERSLIP 6530.TM. available from Micro Powder Inc.;
fluorinated waxes, for example, POLYFLUO 190.TM., POLYFLUO 200.TM.,
POLYSILK 19.TM. and POLYSILK 14.TM. available from Micro Powder
Inc.; mixed fluorinated amide waxes, for example, MICROSPERSION
19.TM. also available from Micro Powder Inc.; imides, esters,
quaternary amines, carboxylic acids, acrylic polymer emulsions, for
example, JONCRYL 74.TM., 89.TM., 130.TM., 537.TM. and 538.TM.
available from SC Johnson Wax; and chlorinated polypropylenes and
polyethylenes available from Allied Chemical, Petrolite Corp. and
SC Johnson. Mixtures and combinations of the foregoing waxes also
may be used in embodiments.
[0084] c. Aggregating Factor
[0085] An aggregating factor (or coagulant) may be used to
facilitate growth of the nascent toner particles and may be an
inorganic cationic coagulant, such as, for example, polyaluminum
chloride (PAC), polyaluminum sulfosilicate (PASS), aluminum
sulfate, zinc sulfate, magnesium sulfate, chlorides of magnesium,
calcium, zinc, beryllium, aluminum, sodium, other metal halides
including monovalent and divalent halides and so on.
[0086] The aggregating factor may be present in an emulsion in an
amount of from, for example, from about 0 to about 10 wt %, from
about 0.05 to about 5 wt % based on the total solids in the
toner.
[0087] d. Surface Additive
[0088] The toner particles can be mixed with one or more of silicon
dioxide or silica (SiO.sub.2), titania or titanium dioxide
(TiO.sub.2) and/or cerium oxide, among other additives. Silica may
be a first silica and a second silica. The second silica may have a
larger average size (diameter) than the first silica. The first
silica may have an average primary particle size, measured in
diameter, in the range of from about 5 nm to about 50 nm. The
second silica may have an average primary particle size, measured
in diameter, in the range of from about 100 nm to about 200 nm. The
titania may have an average primary particle size in the range of
from about 5 nm to about 50 nm. The cerium oxide may have an
average primary particle size in the range of, for example, about 5
nm to about 50 nm.
[0089] Zinc stearate also may be used as an external additive.
Calcium stearate and magnesium stearate may provide similar
functions. Zinc stearate may have an average primary particle size
of from about 500 nm to about 700 nm.
[0090] B. Toner Particle Preparation
[0091] The toner particles may be prepared by any method within the
purview of one skilled in the art, for example, any of the EA
methods can be used with a polyester resin. However, any suitable
method of preparing toner particles may be used, including chemical
processes, such as, suspension and encapsulation processes
disclosed, for example, in U.S. Pat. Nos. 5,290,654 and 5,302,486,
the disclosure of each of which herein is incorporated by reference
in entirety; by conventional granulation methods, such as, jet
milling; pelletizing slabs of material; other mechanical processes;
any process for producing nanoparticles or microparticles; and so
on.
[0092] In embodiments relating to an EA process, a resin, for
example, made as described above, can be dissolved in a solvent,
and can be mixed into an emulsion medium, for example water, such
as, deionized water (DIW), optionally containing a stabilizer, and
optionally a surfactant. Examples of suitable stabilizers include
water-soluble alkali metal hydroxides, such as, sodium hydroxide,
potassium hydroxide, lithium hydroxide, beryllium hydroxide,
magnesium hydroxide, calcium hydroxide or barium hydroxide;
ammonium hydroxide; alkali metal carbonates, such as, sodium
bicarbonate, lithium bicarbonate, potassium bicarbonate, lithium
carbonate, potassium carbonate, sodium carbonate, beryllium
carbonate, magnesium carbonate, calcium carbonate, barium carbonate
or cesium carbonate; or mixtures thereof. When a stabilizer is
used, the stabilizer can be present in amounts of from about 0.1%
to about 5% by weight of the resin. The stabilizer can be added to
the mixture at ambient temperature or can be heated to the mixture
temperature prior to addition.
[0093] Following emulsification, toner compositions may be prepared
by aggregating a mixture of a resin, an optional colorant, an
optional wax and any other desired additives in an emulsion,
optionally, with surfactants as described above, and then
optionally coalescing the aggregated particles in the mixture. A
mixture may be prepared by adding an optional wax or other
materials, which optionally also may be in a dispersion, including
a surfactant, to the emulsion comprising a resin-forming material
or a resin. The pH of the resulting mixture may be adjusted with an
acid, such as, for example, acetic acid, nitric acid or the like.
In embodiments, the pH of the mixture may be adjusted to from about
2 to about 4.5.
[0094] Additionally, in embodiments, the mixture may be homogenized
at a speed from about 600 to about 4,000 rpm. Homogenization may be
by any suitable means, including, for example, an IKA ULTRA TURRAX
T50 probe homogenizer.
[0095] Following preparation of the above mixture, larger particles
or aggregates, often sized in micrometers, formed from the smaller
resin particles, for example, from the initial polymerization
reaction, often sized in nanometers, are obtained. An aggregating
agent may be added to the mixture to facilitate the process.
Suitable aggregating factors or agents include, for example,
aqueous solutions of a divalent cation, a multivalent cation or a
compound comprising same.
[0096] The aggregating factor may be added to the mixture at a
temperature that is below the T.sub.g of the resin or of a
polymer.
[0097] The aggregating factor may be added to the mixture
components to form a toner in an amount of, for example, from about
0.1 part per hundred (pph) to about 1 pph.
[0098] To control aggregation of the particles, the aggregating
factor may be metered into the mixture over time. For example, the
factor may be added incrementally into the mixture over a period of
from about 5 to about 240 minutes.
[0099] Addition of the aggregating factor also may be done while
the mixture is maintained under stirred conditions, in embodiments,
from about 50 rpm to about 1,000 rpm; and at a temperature that is
below the T.sub.g of the resin or polymer. Growth and shaping of
particles following addition of aggregation factor may be
accomplished under any suitable condition(s).
[0100] Particles may be permitted to aggregate until a
predetermined desired particle size is attained. Particle size can
be monitored during the growth process, for example, with a COULTER
COUNTER, for average particle size. Aggregation thus may proceed by
maintaining the mixture, for example, at elevated temperature, or
slowly raising the temperature, for example, from about 40.degree.
C. to about 100.degree. C., and holding the mixture at that
temperature from about 0.5 hr to about 6 hrs, while maintaining
stirring, to provide the desired aggregated particles. Once the
predetermined desired particle size is attained, growth is
halted.
[0101] Once the desired size of the toner particles or aggregates
is achieved, the pH of the mixture may be adjusted with base or
buffer to a value of from about 5 to about 10. The adjustment of pH
may be used to freeze, that is, to stop, toner particle growth. The
base used to stop toner particle growth may be, for example, an
alkali metal hydroxide, such as, sodium hydroxide, potassium
hydroxide, ammonium hydroxide, and the like, and combinations
thereof.
[0102] In embodiments, an agent may be introduced after aggregation
is complete to contribute to pH adjustment. Thus, the agent used
after aggregation is complete may comprise, for example,
ethylenediamine tetraacetic acid (EDTA), gluconal,
hydroxyl-2,2'iminodisuccinic acid (HIDS), dicarboxylmethyl glutamic
acid (GLDA), methyl glycidyl diacetic acid (MGDA),
hydroxydiethyliminodiacetic acid (HIDA), sodium gluconate,
potassium citrate, sodium citrate, nitrotriacetate salt, humic
acid, fulvic acid; salts of EDTA, such as, alkali metal salts of
EDTA, tartaric acid, gluconic acid, oxalic acid, polyacrylates,
sugar acrylates, citric acid, polyaspartic acid, diethylenetriamine
pentaacetate, 3-hydroxy-4-pyridinone, dopamine, eucalyptus,
iminodisuccinic acid, ethylenediaminedisuccinate, polysaccharide,
sodium ethylenedinitrilotetraacetate, thiamine pyrophosphate,
farnesyl pyrophosphate, 2-aminoethylpyrophosphate, hydroxyl
ethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid,
diethylene triaminepentamethylene phosphonic acid, ethylenediamine
tetramethylene phosphonic acid and mixtures thereof.
[0103] The aggregates particles may be of a size of less than about
8 .mu.m, from about 2 .mu.m to about 7 .mu.m, but sizes outside of
those ranges can be used.
[0104] After aggregation, but prior to coalescence, a resin coating
may be applied to the aggregated particles to form a shell
thereover. A shell can comprise any resin described herein, such
as, a rosin resin of interest, or as known in the art. In
embodiments, a polyester amorphous resin latex as described herein
may be included in a shell, which may be combined with a different
resin, and then added to the particles as a resin coating to form a
shell.
[0105] A shell resin may be applied to the aggregated particles by
any method within the purview of those skilled in the art. A resin
emulsion may be combined with the aggregated particles so that a
shell forms over the aggregated particles.
[0106] Formation of a shell over aggregated particles may occur
while heating to a temperature from about 30.degree. C. to about
80.degree. C. Formation of a shell may take place for a period of
time from about 5 minutes to about 10 hours.
[0107] A shell may be present in an amount from about 1% by weight
to about 80% by weight of the toner particle.
[0108] Following aggregation to a desired particle size and
application of any optional shell, the particles then may be
coalesced to a desired final shape, such as, a circular shape, for
example, to correct for irregularities in shape and size.
Coalescence can be achieved by, for example, heating the mixture to
a temperature from about 45.degree. C. to about 100.degree. C.,
which may be at or above the T.sub.g of the resins used to form the
toner particles, and/or reducing the stirring, for example, from
about 1000 to about 100 rpm. Coalescence may be conducted over a
period from about 0.01 to about 9 hr, see, for example, U.S. Pat.
No. 7,736,831.
[0109] Optionally, a coalescing agent can be used. Examples of
suitable coalescence agents include, but are not limited to,
benzoic acid alkyl esters, ester alcohols, glycol/ether-type
solvents, long chain aliphatic alcohols, aromatic alcohols,
mixtures thereof and the like.
[0110] The coalescence agent (or coalescing or coalescence aid
agent) can evaporate during later stages of the EA process, such
as, during a second heating step, that is, generally above the
T.sub.g of the resin or a polymer. The final toner particles are
thus, free of, or essentially or substantially free of any
remaining coalescence agent. To the extent that any remaining
coalescence agent may be present in a final toner particle, the
amount of remaining coalescence agent is such that presence thereof
does not affect any properties or the performance of the toner or
developer.
[0111] The coalescence agent can be added prior to the coalescence
or fusing step in any desired or suitable amount. For example, the
coalescence agent can be added in an amount of from about 0.01 to
about 10% by weight, based on the solids content in the reaction
medium. Amounts outside that range can be used, as desired.
[0112] After coalescence, the mixture may be cooled to RT, such as,
from about 20.degree. C. to about 25.degree. C. Cooling may be
rapid or slow, as desired. A suitable cooling method may include
introducing cold water in a jacket around a reactor. After cooling,
the toner particles optionally may be washed with water and then
dried. Drying may be accomplished by any suitable method for drying
including, for example, freeze drying.
[0113] The toner particles also may contain optional additives.
[0114] The toner may include any known charge additives in amounts
of from about 0.1 to about 10 weight % of the toner. Examples of
such charge additives include alkyl pyridinium halides, bisulfates,
the charge control additives of U.S. Pat. Nos. 3,944,493;
4,007,293; 4,079,014; 4,394,430; and 4,560,635, the disclosure of
each of which herein is incorporated by reference in entirety,
negative charge enhancing additives, such as, aluminum complexes,
and the like.
[0115] Charge enhancing molecules can be used to impart either a
positive or a negative charge on a toner particle. Examples include
quaternary ammonium compounds, see, for example, U.S. Pat. No.
4,298,672, organic sulfate and sulfonate compounds, see for
example, U.S. Pat. No. 4,338,390, cetyl pyridinium
tetrafluoroborates, distearyl dimethyl ammonium methyl sulfate,
aluminum salts and so on.
[0116] Surface additives can be added to the toner compositions,
for example, after washing or drying. Examples of such surface
additives include, for example, one or more of a metal salt, a
metal salt of a fatty acid, a colloidal silica, a metal oxide, such
as, TiO.sub.2 (for example, for improved relative humidity (RH)
stability, tribo control and improved development and transfer
stability), an aluminum oxide, a cerium oxide, a strontium
titanate, SiO.sub.2, mixtures thereof and the like. Examples of
such additives include those disclosed in U.S. Pat. Nos. 3,590,000;
3,720,617; 3,655,374; and 3,983,045, the disclosure of each of
which herein is incorporated by reference in entirety.
[0117] Additives may be in an amount of from about 0.1 to about 10
wt % of the toner particle.
[0118] Other surface additives include lubricants, such as, a metal
salt of a fatty acid (e.g., zinc or calcium stearate) or long chain
alcohols, such as, UNILIN 700 available from Baker Petrolite and
AEROSIL R972.RTM. available from Degussa. Coated silicas of U.S.
Pat. Nos. 6,190,815 and 6,004,714, the disclosure of each of which
herein is incorporated by reference in entirety, also can be
present. An additive can be in an amount of from about 0.05 to
about 5% by weight of the toner particle, which additives can be
added during aggregation or blended into a formed toner
product.
[0119] Toners may possess suitable charge characteristics when
exposed to extreme RH conditions. The low humidity zone (C zone)
may be about 10.degree. C. and 15% RH, while the high humidity zone
(A zone) may be about 28.degree. C. and 85% RH.
[0120] Toners of the instant disclosure also may possess a parent
toner charge per mass ratio (q/m) of from about -5 .mu.C/g to about
-90 .mu.C/g, and a final toner charge after surface additive
blending of from about -15 .mu.C/g to about -80 .mu.C/g.
[0121] Gloss of a toner may be influenced by amount of retained
metal ion, such as, Al.sup.3+, in a particle. Amount of retained
metal ion may be adjusted by addition of a chelator, such as, EDTA.
Amount of retained metal ion, for example, Al.sup.3+, in toner
particles of the present disclosure may be from about 0.001 pph to
about 1 pph. The gloss level of a toner of the instant disclosure
may have a gloss, as measured by Gardner device, of from about 20
gloss units (gu) to about 100 gu.
[0122] Other desirable characteristics of a toner include storage
stability, particle size integrity, high rate of fusing to the
substrate or receiving member, sufficient release of the image from
the photoreceptor, nondocument offset, use of smaller-sized
particles and so on, and such characteristics can be obtained by
including suitable reagents, suitable additives or both, and/or
preparing the toner with particular protocols.
[0123] The characteristics of the toner particles may be determined
by any suitable technique and apparatus. Volume average particle
diameter and geometric standard deviation may be measured using an
instrument, such as, a Beckman Coulter MULTISIZER 3, operated in
accordance with the instructions of the manufacturer.
[0124] Dry toner particles, exclusive of external additives, may
have the following characteristics: (1) volume average diameter
(also referred to as "volume average particle diameter") of from
about 2.5 to about 20 .mu.m; (2) number average geometric standard
deviation (GSD.sub.n) and/or volume average geometric standard
deviation (GSD.sub.v) of from about 1.18 to about 1.30; and (3)
circularity of from about 0.9 to about 1.0 (measured with, for
example, a Sysmex FPIA 2100 analyzer).
[0125] Developers
[0126] The toner particles thus formed may be formulated into a
developer composition. For example, the toner particles may be
mixed with carrier particles to achieve a two component developer
composition. The toner concentration in the developer may be from
about 1% to about 25% by weight of the total weight of the
developer, with the remainder of the developer composition being
the carrier. However, different toner and carrier percentages may
be used to achieve a developer composition with desired
characteristics.
[0127] 1. Carrier
[0128] Examples of carrier particles for mixing with the toner
particles include those particles that are capable of
triboelectrically obtaining a charge of polarity opposite to that
of the toner panicles. Illustrative examples of suitable carrier
particles include granular zircon, granular silicon, glass, steel,
nickel, ferrites, iron ferrites, silicon dioxide, one or more
polymers and the like. Other carriers include those disclosed in
U.S. Pat. Nos. 3,847,604; 4,937,166; and 4,935,326.
[0129] The carrier particles may include a core with a coating
thereover, which may be formed from a polymer or a mixture of
polymers that are not in close proximity thereto in the
triboelectric series, such as, those as taught herein or as known
in the art. The coating may include fluoropolymers. The coating may
have a coating weight of, for example, from about 0.1 to about 5%
by weight of the carrier.
[0130] Various effective suitable means can be used to apply a
polymer to the surface of the carrier core, for example, cascade
roll mixing, tumbling, milling, shaking, electrostatic powder cloud
spraying, fluidized bed mixing, electrostatic disc processing,
electrostatic curtain processing, combinations thereof and the
like. The mixture of carrier core particles and polymer then may be
heated to enable the polymer to melt or to fuse to the carrier
core. The coated carrier particles then may be cooled and
thereafter classified to a desired particle size.
[0131] Devices Comprising a Toner Particle
[0132] Toners and developers can be combined with a number of
devices ranging from enclosures or vessels, such as, a vial, a
bottle, a flexible container, such as a bag or a package, and so
on, to devices that serve more than a storage function, such as, a
toner delivery device, such as, a cartridge, for forming an image.
Blocking performance can be manifest as storage stability as a
finely divided powder.
[0133] Imaging or Forming Devices
[0134] The toners or developers can be used for electrostatographic
or electrophotographic processes, including those disclosed in U.S.
Pat. No. 4,295,990, the disclosure of which herein is incorporated
by reference in entirety. Any known type of image development
system may be used in an image developing device, including, for
example, magnetic brush development, jumping single component
development, hybrid scavengeless development (HSD) and the like.
Those and similar development systems are within the purview of
those skilled in the art.
[0135] Imaging processes include, for example, preparing an image
with an electrophotographic device including, for example, one or
more of a charging component, an imaging component, a
photoconductive component, a developing component, a transfer
component, a fusing component and so on. The device may include a
high speed printer, a color printer and the like.
[0136] Once the image is formed with toners/developers via a
suitable image development method, such as any of the
aforementioned methods, the image then may be transferred to an
image receiving medium or substrate, such as, a paper and the like.
In embodiments, the fusing member or component, which can be of any
desired or suitable configuration, such as, a drum, a roller, a
belt, a web, a flat surface, a platen or the like, may be used to
set the toner image on the substrate. MFT is a consideration as the
minimum temperature needed to affix images comprising toner on a
substrate. Blocking performance can be a consideration as the
temperature which can result in unintended transfer of a fixed or
fused image or parts thereof from a substrate carrying the image to
another substrate.
[0137] Color printers commonly use four housings carrying different
colors to generate full color images based on black plus the
standard printing colors, cyan, magenta and yellow. In embodiments,
additional housings may be desirable, including image generating
devices possessing five housings, six housings or more, thereby
providing the ability to carry additional toner colors to print an
extended range of colors (extended gamut).
[0138] Thermoplastic and thermosetting polymers can be used for 3-D
printing by any of a variety of materials and methods, such as,
selective heat sintering, selective laser sintering, fused
deposition modeling, robocasting and so on. A resin can be formed
into sheets for use in laminated object manufacturing. In
embodiments, a resin can be configured as a filament. Granular
resin can be used in selective laser melting methods. Ink jet
devices can deliver resin.
[0139] Examples of polymers include acrylonitrile butadiene
styrene, polyethylene, polymethylmethacrylate, polystyrene and so
on. In embodiments, polymers can be mixed with an adhesive to
promote binding. In embodiments, an adhesive is interleaved with a
layer of cured or hardened polymer to bind leafs or layers.
[0140] A polymer may be configured to contain a compound that on
exposure to a stimulant decomposes and forms one or more free
radicals, which promote polymerization of monomers of a polymer of
interest, such as, forming branches, networks and covalent bonds.
For example, a polymer can comprise a photoinitiator to induce
curing on exposure to white light, an LED, UV light and so on. Such
materials can be used in stereolithography, digital light
processing, continuous liquid interface production and so on.
[0141] Waxes and other curing material can be incorporated into a
3-D composition or can be provided as a separate composition for
deposition on a layer of a resin of interest or between layers of a
resin of interest.
[0142] For example, a selective laser sintering powder, such as, a
polyacrylate or polystyrene, is placed in a reservoir atop of a
delivery piston. Granular resin is transferred from the reservoir
to a second void comprising a fabrication piston which carries the
transferred resin in the form of a thin layer. The thin layer is
then exposed to a light or a laser tuned to melt and to fuse
selected sites of the layer of resin particles. A second layer of
resin granules is added from the reservoir to the fabrication void
and the laser again melts and fuses selected portions of the layer
of granules. The heating and fusion is of an intensity and strength
to enable heating and fusing of sites from the second layer to
sites of the first layer, thereby forming a growing solid structure
in the vertical direction. In embodiments, an adhesive is applied
to the fused first layer before the unfused granular resin for the
second layer is applied. When completed, the unfused resin powder
is removed leaving the fused granules in the form of a designed
structure. Such a manufacturing method is an additive process as
successive layers of the structure are laid down consecutively.
[0143] Toner herein can be can be used to manufacture articles,
such as, sensors, materials with solvent switchable electronic
properties, optical limiters and filters, and optical data storage
devices. Plasmonic properties of metals enable bioimaging because,
contrary to commonly used fluorescent dyes, nanoparticulate metal
does not undergo photobleaching and can be used to monitor dynamic
events over an extended period of time.
[0144] The following Examples illustrate embodiments of the
disclosure. The Examples are illustrative only and are not intended
to limit the scope of the present disclosure. Parts and percentages
are by weight unless otherwise indicated.
EXAMPLES
Example 1
Reaction Products of Rosin Acid with Glycerine Carbonate
[0145] To a one liter Parr 4020 reactor equipped with a mechanical
stirrer were added glycerine carbonate (130 g, 1.1 mole),
tetraethyl ammonium iodide (1.285 g, 0.005 mole) and dehydroabietic
acid (DHAA) (100.1 g, 0.33 mole). The mixture was heated to
150.degree. C. under a nitrogen atmosphere and after two hours,
additional DHAA (200.3 g, 0.67 mole) was added over a 2 hr period.
The temperature was maintained at 150.degree. C. for an additional
8 hours until an AV of <1.0 mg KOH/g was attained, which relates
to >95% conversion of reagents into a polyester polymer.
[0146] Two grams of reaction products were subjected to high
pressure liquid chromatographic (HPLC) separation using ethyl
acetate (25%) and hexanes (75%) as eluent. Bis-rosin alcohols III
and IV and carbonate V were separated and identified by proton
nuclear magnetic resonance (NMR), C.sup.13 NMR and mass
spectroscopy. The mixture of rosin-diols I and II was complexed
with copper (II) chloride, separated and regenerated with ammonia
to rosin-diols I and II, respectively, and characterized by proton
NMR, C.sup.13 NMR and mass spectroscopy. The relative ratios of
rosin adducts I through V were determined by HPLC. The HPLC was
performed with a Synergi RP-Polar C.sup.18 column using a mobile
phase mixture of 20% water, 0.1% trifluoroacetic acid, 40%
acetonitrile and 40% tetrahydrofuran with a flow rate of 1 ml/min,
with a run time of 10 min and using a UV detector.
Examples 2-5
Reaction Products of Rosin Acid with Glycerine Carbonate
[0147] The method of Example 1 was practiced with reagent amounts
and reaction conditions varied as provided in Table 1.
TABLE-US-00001 TABLE 1 Glycerine Rosin Ex- Carbonate Temp. Catalyst
Adduct (% wt) Ratio ample (mole) .degree. C. mol % I/II III IV V
I/II/V:III/IV 1 1.1 150 0.5 64 14 6 15 4:1 2 1.1 165 0.5 44 21 18
15 1.5:1 3 1.1 150 18 62 12 5 13 4.2:1 4 1.1 165 18 56 12 8 9 3.2:1
5 3.0 160 0.5 85 1 4 10 19:1
Example 6
Synthesis of Bio-Based Resin with 8 mol % of Rosin
[0148] To a 2 Liter Buchi reactor were added 220 g of hydrogenated
rosin acid (8 mol %), 90 g glycerin carbonate GC) and 3 g of
tetraethyl ammonium bromide (TAB). The mixture was heated to
170.degree. C. and maintained for 16 hours until the AV was less
than 1 mg/g KOH. To that mixture in the same reactor were added
118.92 g of 1,4-butanediol (BD), 185.7 g of propylene glycol (PG),
528.96 g of isophthalic acid (IPA), 15.66 g of succinic acid (SA)
and 3 g of FASCAT 4100. The mixture then was heated to 220.degree.
C. over a 6 hr period and maintained overnight. Thereafter, the
mixture was held under vacuum at 225.degree. C. until the desired
T.sub.g was obtained, 122.7.degree. C., and the resin had an AV of
10.27 mg/g KOH.
Example 7
Synthesis of Bio-Based Resin with 6 mol % of Rosin
[0149] To a 2 Liter Buchi reactor were added 150 g of hydrogenated
rosin acid, 70 g GC and 3 g of TAB. The mixture was heated to
170.degree. C. and maintained for 16 hours until the AV was less
than 1 mg/g KOH. To that mixture in the same reactor were added
118.92 g of BD, 185.7 g of PG, 528.96 g of IPA, 15.66 g of SA and 3
g of FASCAT 4100. The mixture then was heated to 220.degree. C.
over a 6 hour period and maintained overnight. Thereafter, the
mixture was held under vacuum at 225.degree. C. until the desired
T.sub.g was obtained, 122.7.degree. C., and the resin had an AV of
10.27 mg/g KOH.
Example 8
Toner with 8 mol % Rosin Resin and C10:C9 CPE
[0150] Into a 2 liter glass reactor equipped with an overhead mixer
were added 290.82 g of the resin from Example 6, 26.46 g of C10:C9
CPE resin emulsion (31.46 wt %), 36.50 g of IGI wax dispersion
(30.33 wt %) and 43.36 g cyan pigment, PB15:3 (16.59 wt %). Then,
2.15 g of Al.sub.2(SO.sub.4).sub.3 (27.85 wt %) were added under
homogenization. The mixture was heated to 38.9.degree. C. to
aggregate the particles while stirring at 300 rpm. Particle size
was monitored with a COULTER COUNTER until the particles reached a
volume average particle size of 5.54 .mu.m, GSD.sub.v of 1.18.
Thereafter, the pH of the reaction slurry was increased to 8.3
using 4 wt % NaOH solution followed by 4.62 g EDTA (39 wt %) to
freeze toner growth. After freezing, the reaction mixture was
heated to 76.5.degree. C. for 3 hours resulting in a final particle
size of 5.42 .mu.m, GSD.sub.v of 1.21, GSD.sub.n of 1.23 and
circularity of 0.972. The toner slurry then was cooled to RT,
separated by sieving (25 .mu.m), filtered, washed and freeze
dried.
Example 9
Toner with 8 mol % Rosin Resin and C10:C6 CPE
[0151] The process of Example 8 was repeated except 24.08 g of
C10:6 CPE emulsion (34.56 wt %) were used instead of the C10:9
resin emulsion.
[0152] The resulting toner had an average particle size of 5.90
.mu.m, GSD.sub.v of 1.24, GSD.sub.n of 1.23 and circularity of
0.969.
Example 10
Toner with 6 mol % Rosin Resin and C10:6 CPE
[0153] The process of Example 9 was repeated except the bioresin of
Example 7 comprised of 6 mol % of rosin was used.
[0154] The resulting toner had an average particle size of 5.83
.mu.m, GSD.sub.v of 1.23, GSD.sub.u of 1.23 and circularity of
0.971.
Example 11
Toner Analysis
[0155] The toners were analyzed for various properties. Two cyan
toners were used as controls. Control Toner 1 is comprised of a
polystyrene-acrylate resin and does not contain a CPE resin.
Control Toner 2 is comprised of a non-biobased amorphous polyester
resin and CPE C10:C9.
[0156] The structural properties of the five toners were similar,
Table 2.
TABLE-US-00002 TABLE 2 Toner Properties Control 1 Control 2 Example
8 Example 9 Example 10 Rosin- -- -- 8% 8% 6% Resin CPE -- 6.8% 6.8%
6.8% 6.8% (10:9) (10:9) (10:6) (10:6) Wax 9% 9% 9% 9% 9% Size
(.mu.m) 5.90 5.8 5.42 5.90 5.83 GSD (v/n) 1.21/1.21 1.22/1.21
1.21/1.23 1.23/1.23 1.23/1/23 Circ 0.968 0.969 0.972 0.969
0.971
[0157] Fusing parameters, such as, MFT (minimum fixing temperature)
and hot offset, of the above prepared toners were collected with
samples of the particles fused onto Color Xpressions Select (90
gms) paper using a fusing fixture similar to that of the commercial
Xerox 700) printer. Fixing latitude is the difference of hot offset
and MFT, that is, MFT subtracted from hot offset temperature.
TABLE-US-00003 TABLE 3 Fusing and Blocking Properties of Toners
Control 1 Control 2 Example 8 Example 9 Example 10 Gloss at 19.7
31.8 27.3 10.1 9.9 MFT Hot Offset >210 200 >210 >210
>210 (.degree. C.) MFT 139 125 125 120 125 (.degree. C.)
Latitude >71 75 >85 >90 >85 (.degree. C.) Blocking 53
54 54 49 54 (.degree. C.)
[0158] Control toner 1 has a high MFT of 139.degree. C. and good
blocking, whereas control toner 2 with the more expensive CPE C10:9
has a lower MFT of 125.degree. C. and good blocking. Thus, CPE
lowers MFT. The toner of Example 8 with a biobased resin with 8 mol
% rosin and the more expensive CPE C10:9, also resulted in a lower
MFT of 125.degree. C. and good blocking, demonstrating that a
bioresin can be used in toner and higher amounts of rosin in a
resin can be used with larger CPE's. The toner of Example 9 with
biobased resin comprising 8 mol % rosin and the lower cost CPE
C10:6 also resulted in a lower MFT of 120.degree. C., but had poor
blocking of 49.degree. C. On the other hand, the toner of Example
10 with biobased resin comprising 6 mol % rosin and the lower cost
CPE C10:6 resulted in both a low MFT of 125.degree. C. and good
blocking of 54.degree. C. Therefore, unexpectedly, a lower cost
toner with good blocking and low fixing temperature made from
sustainable materials was obtained with a particular amount of the
rosin component in a resin and lower cost, smaller, crystalline
polyester resins.
[0159] It will be appreciated that various of the above-disclosed
and other features and functions, or alternatives thereof, may be
combined into other different systems or applications. Changes,
modifications and the like can be made to the teachings herein
without departing from the spirit and scope of the subject matter
of interest. Also various presently unforeseen or unanticipated
alternatives, modifications, variations or improvements therein may
be subsequently made by those skilled in the art, which are also
intended to be encompassed by the following claims. Unless
specifically recited in a claim, steps or components of claims
should not be implied or imported from the specification or any
other claims as to any particular order, number, position, size,
shape, angle, color or material.
[0160] All references cited herein are incorporated herein by
reference in entirety.
* * * * *